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郑州大学张懿强缺电子胺实现卤化物锚定氢键,助力稳定宽禁带钙钛矿及钙钛矿/有机叠层太阳能电池

  • 2026-04-16 04:04:06
郑州大学张懿强缺电子胺实现卤化物锚定氢键,助力稳定宽禁带钙钛矿及钙钛矿/有机叠层太阳能电池

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‍大家好，欢迎关注和星标钙钛矿学习与交流！钙钛矿 / 有机叠层太阳能电池（TSCs）是实现高效率、溶液加工型光伏器件的重要技术路线；然而，宽禁带（WBG）钙钛矿子电池中因卤化物相分离及伴随的离子迁移引发的电压损失，仍制约着这类器件的性能提升。郑州大学张懿强团队通过理性分子设计制备氢键调控剂，精准调控钙钛矿结晶动力学，成功攻克这一难题。相关工作于2026年4月2日在《Angewandte Chemie International Edition》发表题为：Electron-Deficient Amines Enable Halide-Anchoring Hydrogen Bonding for Stable Wide-Bandgap Perovskites Toward Perovskite/Organic Tandem Solar Cells的研究成果！研究人员将吸电子性砜基（-SO₂）引入二氨基芴，使氨基（-NH₂）的化学功能从阳离子配位碱被电子重构成靶向卤离子的氢键供体，并通过定向N-H···Br⁻相互作用选择性稳定溴离子。这种缺电子分子结构可稳定富溴的 DMSO-PbBr₂/DTD 前驱体中间体，抑制富溴相过早成核，促进成膜过程中卤离子在水平与垂直方向的均匀分布；同时，该结构还能提高宽禁带钙钛矿中卤离子迁移的活化能垒。基于此策略，1.85 eV 宽禁带单结钙钛矿太阳能电池实现了 19.32% 的最高光电转换效率（PCE），且在持续光照下的工作稳定性显著提升。将其应用于钙钛矿 / 有机叠层太阳能电池后，器件最高光电转换效率达26.76%，开路电压（Vₒc）为 2.216 V，处于已报道钙钛矿 / 有机叠层电池的顶尖水平。本研究阐明了宽禁带钙钛矿中卤化物化学的分子调控构效关系范式，为制备相稳定、高电压的叠层光伏器件提供了可推广的技术路径。

器件性能和制备工艺

器件结构
ITO/NiOₓ/4PADCB/FA₀.₈Cs₀.₂Pb(I₀.₅Br₀.₅)₃/PDAI/C₆₀/BCP/Ag
组分
FA₀.₈Cs₀.₂PbI₁.₅Br₁.₅；1 mL DMF:DMSO 混合溶剂中含：CsI 52.0 mg、FAI 137.6 mg、PbI₂ 115 mg、PbBr₂ 275 mg、KSCN 1 mg
添加剂
DTD（二氨基二苯并噻吩砜）、KSCN
带隙
1.85 eV
PCE
19.32%
VOC
1.377 V
JSC
16.74 mA·cm⁻²
FF
83.81%
溶剂
DMF:DMSO = 4:1（体积比）
反溶剂
氯苯（CB）
旋涂
4000 rpm，45 s
反溶剂滴加时间
旋涂结束前 10 s
空穴传输层材料
NiOₓ、4PADCB
空穴传输层工艺
4PADCB（0.5 mg/mL 乙醇溶液），4000 rpm 旋涂 30 s，100 ℃退火 10 min
上界面钝化材料
PDAI₂（1,3 - 丙二胺二氢碘酸盐）
上界面钝化工艺
PDAI（1 mg/mL 异丙醇溶液），4000 rpm 动态旋涂 30 s，100 ℃退火 10 min
电子传输层
C₆₀（20 nm）、BCP（7 nm），真空蒸镀

分子设计核心思路

  • 设计对象：二氨基二苯并噻吩砜（DTD）
  • 改性基团：强吸电子砜基（-SO₂）
  • 作用原理：砜基降低氨基 N 原子电子云密度，增强 N-H 键极性，将氨基从阳离子配位碱转化为卤靶向氢键供体，形成定向 **N-H・・・Br⁻** 氢键。

图文速览

作者：Shiheng Wang, Qiqi Wang, Xiaolan Lu, Tangyue Xue, Jing Yang, Ruiqing He, Xing Gao, Jie Pan, Xianglong Sun, Junru Chen, Jinyang Song, Jian Cheng, Gang Li, Yanlin Song, Yiqiang Zhang

查看原文（点击底部阅读原文跳转）：

https://doi.org/10.1002/anie.9708831

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  1. CONNECT:[ UseTime:0.001052s ] mysql:host=127.0.0.1;port=3306;dbname=i460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.001072s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.000700s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.001570s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.001392s ]
  6. SELECT * FROM `set` [ RunTime:0.000531s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.001483s ]
  8. SELECT * FROM `article` WHERE `id` = 508972 LIMIT 1 [ RunTime:0.001035s ]
  9. UPDATE `article` SET `lasttime` = 1778059690 WHERE `id` = 508972 [ RunTime:0.001435s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 64 LIMIT 1 [ RunTime:0.000748s ]
  11. SELECT * FROM `article` WHERE `id` < 508972 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.002446s ]
  12. SELECT * FROM `article` WHERE `id` > 508972 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.001417s ]
  13. SELECT * FROM `article` WHERE `id` < 508972 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.005115s ]
  14. SELECT * FROM `article` WHERE `id` < 508972 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.003304s ]
  15. SELECT * FROM `article` WHERE `id` < 508972 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.003292s ]
0.189322s